Polymerization of olefins



o. A. BROWN 2,424,143

POLYMERIZATION OF OLEFINS July 15, 1947.

Filed Aug. '7, 1944 I 21 3| SeHler 26 29 Discard Acid 22 l 34 I6 I Absorber Fresh Acid Absorber I as cooler 55 Cooler |a ix h g Fl WM 1 1e 2o '4 Secondary Tertiary Olefin Feed Olefin Feed -Q gyms! 2| i Hecier l5 --i 2 Acid Exiruct Acid Exiracf 23 cf? 52 4e Absorber Absorber 6| 43 r v '49 l 42 Cooler 59 48 Tania y Sacondary Olefin eed Olefin Faed -Q- I 50 v 4 Acid Extraci f 6 5 a I 57 Acmemuce sefller c He ts Fresh Acid IIIH 6 Cooler \-T. v' b,

43 4 Palyiner Th4 qr W M JNVENroR.

' Discord Acid ATTORNEY.

Pafented July 15, 1947 Orval A. Brown, Baytown, Tex,

assignor to Standard Oil Development Company, a co r-.

poration of Delaware Application August 7, 1944, Serial No. 548,442

The present invention is directed to a process forco nducting; reactionsbetween different olefins which are usually designated as interp ol-ymerization reactions in distinction tothe combination or like olefins which is termed copolymerization. The invention is directed particularly to a process for lnterpolymerizmg secondary oleiins with tertiary olefins in the presence of a liquid catalyst to form a higher hoiling polymer.

The polymerization of olefins in the presence of a liquid catalyst is well known tothe art but heretofore no satisfactory process was known for directingthe reactions to yield predominantly an interpolymer including a plurality of olefins of dissimilar molecular weights and having a molecular weight substantially greater than the sum of two molecules of the olefin feed to the process. As an example, it has been common to treat a hydrocarbon mixture of isobutylene, normal butylene and propylene with hot sulfuric acid but since the tertiary olefin is the more readily polymerized a result of such a treatment is the formation of a major portion of octenes and a minor portion of heptenes. Similarly, the treatment of mixtures of isobutylene and propylene with hot sulfuric acid also results in a product comprising a major portion of iso-octenes and a minor portion of isoheptenes. Since large amounts of secondary olefin, such as propylene, are often available for polymerization, it is desirable to control polymerization reactions to produce an interpolyrner including a secondary olefin and a tertiary olefin. In addition there is a substantial demand for hydrocarbons suitable as a base stock for high octane safety aviation fuel with a boiling point from 300 F. upwardly and such material is not usually formed'by the interpolymerization of only two of the molecules of the olefins commonly available for polymerization reactions.

In accordance with the; present invention, polymerization reactions between olefins are controlled to obtain a polymer including a secondary olefin and a tertiary olefin and having a molecular weight greater than the sum of the molecular weight of a molecule of the secondary olefin and a single molecule of; the tertiary olefin. lhe polymerls particularly suitable for use as a base stock for a safety aviation grade fuel after hydrogenation. Examples of tertiary olefins which may be used in the process of the present invention are isobutylenes, isopentylenes and isohexylenes, and examples of. suitable secondary olefins are propylone, normal butylenes. normal pentylenes and normal hexylenes'. Because of the availability of substantial amounts of the tertiary olefin. isobutyiene, and the secondary olefins, propylene and pent-ylene, the present invention is particularly adapted for the formation of a polymer including lsobutylene, and propylene or pentylene. The present invention may be described briefly 6 Claims. (01. zetaesa s) as including the forming of an extract of a ter: fiery; l fin in a i u d c alyst und r temper ture ondition to prevent s bstan ial cor yme izar tion of the tertiary olefin in the extract, the; fortion f anot ex a t. nclud n a se onda y olefin i a liquid catalyst underconditions to prevent substantial copolymerization ofthe secondary olefin in the extract, and the adjustment oi the temperature of one or both ext actswith a subsequent admixture: thereof to cause the for mationof a polymer of a molecular weight greater than the sum of the molecular weight of the secondary olefin and the molecular weight of ter-. tiary olefin.

In the practice of the present invention, it is usually desirable to. maintain the. tertiary olefin at. a emperature be ow normal Qm' mnetah re and to. f rm, the xt act o a secon ary ol fin e se rme a nm'o Zmat'el oom emea u e with su s quent heat n o the: e tr o h sec ndar olefin t .mn'er tur of t e ord f n he .eqm xture'of thetertiaryelefi th? heated t a o th sec ndar olefin. As a variation of this procedure, the extract. of the secondaryolefin in a liquid Ioatalyst may'ijrst be formed and divided into a minor portionfand ajor portion th mi o liq ti t m y b fl ooled n e fi t ab orb thef e t ar ol fi and t il po on ma b h a ed and this heated portion admixed with the cooled portion which a ns th se on ry and, t tia y oleflns to c u e t e m t n of an i e pql mer nc ud n b t secqnd y edtert rr o finst. s r i r to em lo su r c a id of a strength in the range of 50 to 80. per cent as the iq i atalyst f th inter ol me atlon .re c: tion of the present invention. When forming. the

extr ct of sec n r olefin n u f r a id; the

mp ratu f the u c a ma e in h n e of 0 t F- E en t the h he t tame e in thi ran e there s little appreciab e 9 Yl rimtiQn Q he. secon a y finn, he formati n. 0f the x ac o the ter iary o efi in ri acid, i is suall desirable t e l y a om w at ow ran e o temperatu e cr he id an r fe abl t maintain the t mperatu e of the acid within the range of 30 to 50 F. It will be understood, however, that the formation f th po y ee of the. te iary olefin is a n tion of time as well as the'ternperature of the a d and i s pos ble t employ'ac at a em: perature as great as 125 IE1; in forming the extract of ar ol fin b h n em loy n a temsm of th rder i is de able t at t e resultant extract be used promptly to form the inter polymer. After the two. extraots are formed, it is desirable to increase the temperature of the extract of the secondary olefin in the liquid cata- W to a ran e of 1. 0 t 25 F. a to tame with this hotextract the cool extract of the tertiary olefin in liquid catalyst while maintaining the temperature of the admixture in the range of 150 to 250 F. to cause the formation of the interpolymer. In the mixing zone the amount of secondary olefin should be relatively large in comparison to the amount of tertiary olefin so that the molecules of the more readily polymerizable tertiary olefin are substantially separated and dispersed in a large excess of the less readily polymerizable secondary olefin. It is also desirable to disperse the extract of the tertiary olefin rapidly in the extract of the secondary olefin so that the tertiary olefin is dispersed in,

the heated secondary olefin extract before the molecules of the tertiary olefin have time to copolymerize.

It will be understood that the present invention may be practiced either as a continuous process was a batch process. In the batch process the'feed materials are added intermittently and the product is removed intermittently, whereas, in a continuous process the charge stock is added continuously and the product is removed continuously. It is also to be understood that if desired the extract including the secondary olefin may be formed into a large pool and the extract of the tertiary olefin added to the large pool and product removed therefrom with the charge material added to and the product removed from the pool either continuously or intermittently, as desired, or, alternatively, a stream of extract of tertiary olefin may be contacted with the stream of extract of secondary olefin and the components of the admixture allowed to react while continuing in motion as a stream and the resulting interpolymer subsequently separated from the stream.

Preferred modifications of the present invention will now be described in conjunction with 4 moved from the top of the absorber through outlet IS.

A hydrocarbon fraction including propane and propylene is led through inlet l1 into the lower portion of a second absorber vessel 18 and is allowed to flow upwardly therein countercurrent to a stream of sulfuric acid which is introduced into an upper portion of the vessel through inlet 19 and flows downwardly through the vessel. The sulfuric acid introduced into the absorption vessel through line 19 is preliminarily cooled by cooler. 20 to a temperature of approximately F. and if desired a suitable temperature regulating means, such as cooling coils or jackets, not shown, may be applied to tower 18 in order to maintain a desired temperature in this tower. The extract of the secondary olefin, propylene, in sulfuric acid, is removed from the bottom of tower l8 via line 2| and the unabsorbed hydrocarbons are removed'from the top of the tower via outlet 22. The extract of the secondary olefin in sulfuric acid is passed from line 21 to heater 23 where it is heated to a temperature in the range of 150 F. to 300 F. and is subsequently discharged into mixing vessel 24 which may be provided with heating coil 25 to maintain a suitable temperature therein. The extract of tertiary olefin in sulfuric acid is introduced into mixin vessel 24 by means of line l5 and is thoroughly and rapidly admixed with the extract of the secondary olefin therein. While the components are being admixed, the temperature within vessel 24 is maintained at a suitable level to cause the formation of aninterpolymer including secondary and tertiary olefins so that in effect the heating of the tertiary olefin extract and its admixture with the secondary olefin extract take place simultaneously. The amounts of the two extracts introduced into Vessel 24 are adjusted to maintain a large excess of secondary olefin over that required to combine chemically with the tertiary trating the formation of an extract including secondary olefin and a separate extract including tertiary olefin withthe admixture of the two extracts, and

Figure 2 illustrates a modification in which an extract of secondary olefin is formed and divided into two portions, with one portion heated and another portion cooled and used to absorb tertiary olefins and the two portions then admixed under conditions to cause the formation of an interpolymer.

Turning now specifically to the drawing, and first to Figure 1, inlet ll conducts a mixture of isobutylene, normal butylene and butanes into a suitable absorption column 12 where it is contacted with '70 per cent sulfuric acid introduced into an upper portion of the column via inlet l3. The sulfuric acid introduced into the column is preliminarily cooled by cooler M to a temperature below which substantial polymerization of the tertiary olefins in the feed hydrocarbons will occur. It will be found desirable to maintain the temperature of the sulfuric acid in column l2 at approximately 40 F. If desired, the absorber may be equipped with cooling coils or a jacket, not shown, to aid in the maintenance of a desirable temperature in this vessel. The sulfuric acid flows downwardly through absorber l2 countercurrent to the upwardly flowing stream of gases and absorbs isobutylene therefrom. The resultant isobutylene extract in sulfuric acid is removed from the bottom of the absorber via line l5 and the unabsorbed hydrocarbons are reolefin in order to control more satisfactorily the direction of the reaction and to insure the formation of a polymer including secondary and tertiary olefins rather than the formation of a copolymer of tertiary olefin.

From vessel 24 the admixture is withdrawn through line 26 to settling vessel 21 where it is allowed to separate under the influence of gravity into a heavier acid layer and a lighter hydrocarbon layer. The hydrocarbon layer is removed from an upper portion of vessel 21 through line 28 and is passed into a fractionating column 29 provided with heating means 30. In the fractionating column the unreacted feed hydrocarbons are removed as overhead through line 3| and may be recycled to the system by means, not shown, while the higher boiling polymer is removed through line 32, r

The acid accumulating in the lower portion of settler 27 may be withdrawn through line 33 and recirculated to lines l3 and [9 to act as absorption liquid for additional tertiary olefin and secondary olefin in-towers I2 and I8, respectively. Usually it will be desirable to maintain the acid strength at a predetermined concentration'and a convenient method for accomplishin this is by the continuous withdrawal of a portion of the acid through outlet 34 and the continuous admixture of fresh acid into line 33 by means of inlet 35.

Another modification of the present invention may be practiced in the apparatus shown in Figure 2. In this figure, a propane-propylene fraction is introduced via line 4| into the lower portion of absorber tower 42 and is allowed to'fiow upwardly therein countercurrent to a stream of sulfuric acid introduced into the upper end of the tower through inlet 43. It ispreferre to employ 70 per cent sulfuric acid as the absorbent medium to tower 42 and to cool preliminarily the acid to a temperature approximately 60 F, in cooler 44 before introducing it into the tower. If desired, suitable temperature regulating means, such as cooling coils of a jacket, not shown, may be employed. to regulate the temperature within tower 42. An extract of propylene and sulfuric acid is removed from the bottom of the tower via line 45 and unabsorbed gases are removed'from the top of the tower by outlet 46.

The stream of propylene-sulfuric acid extract in line 45 is split with a minor portion being diverted through branch line 41 containing cooler 48 where it is cooled to a temperature of approximately 40 F. The cooled propylene-sulfuric acid extract is then discharged into the upper end of a second absorption tower 49 where it is allowed to flow downwardly countercurrent to a rising stream of gases. A mixture of isobutylene, normal butylene and butanes is introduced into the lower portion of tower 49 via inlet 50 and fiows upwardly countercurrent to the propylene-sulfuric acid extract. The isobutylene is absorbed from the gaseous mixture to form an extract of isobutylene and propylene-sulfuric acid and thi extract is removed from the bottom of tower 49 through line The unabsorbed hydrocarbons are discharged from the top of tower 49 through outlet 52. I I

The major portion of the propylene-sulfuric acid extract in line 45 is passed into line 52a and through heater 53 where it is heated to a temperature in the range of 150 to 300 F. and the hot extract is then discharged into mixing vessel 54. The chilled extract including isobutylene, propylene and sulfuric acid through line 5! is also discharged into mixing vessel 54 and is admixed rapidly and intimately with the propylenesulfuric acid extract. If desired, the temperature within mixing vessel 5! may be regulated by heating coil 55. It will be evident that since the major portion of the propylene-sulfuric acid extract from tower 42 is passed through heater 53 and into the mixing vessel that the mixing vessel contains a large excess of secondary olefin over that required to combine chemically with the tertiary olefin. The temperature of the components within mixin vessel 54 is sufficiently great to cause the formation of a interpolymer including secondary and tertiary olefin so that in effect the heating of the tertiary olefin in the extract and its admixture with the large excess of secondary olefin within vessel 54 take place simultaneously.

From vessel 54 the mixture is withdrawn through line 56 to a settling vessel 5'! where it is allowed to separate under the influence of gravity into a heavier acid layer and a lighter hydrocarbon layer. The hydrocarbon layer is removed through line 58 and passed into a fractionating column 59 provided with a heating means 60. In the fractionating column the unreacted feed hydrocarbons may be removed as overhead through line 6| and may be recycled to the process by a suitable means, not shown, and the higher boiling polymer may be removed through line 62. The acid accumulated in the lower portion or settler 51 may be withdrawn through line 43 and recirculated in cooler 44 and back to absorption tower 42. In order to maintain the acid strength of a predetermined 6 concentration a portion of the acid may be withdrawn through line 63 and fresh acid added by inlet 64. v

The present invention will be further illustrated by reference to a specific operation in which extracts of a tertiary olefin and a secondar olefin were polymerized.

A secondary olefin, in this instance propylene predominately, was formed in an extract with sulfuric acid. The pro ylene fraction had a composition as follows:

A fraction having this composition was contacted with 20% sulfuric acid at a temperature between and 70 F. for approximately 60 minutes under conditions of good agitation. Approximately 9.5 volumes of the aforementioned hydrocarbon fraction was contacted with 5 volumes or the sulfuric acid. After the period of contact mentioned, agitation was stopped and the acid extract layer separated from the hydrocarbon layer. This extract was then stored for handling in a manner which will be described subsequently.

In a similar manner to the preparation o the propylene extract an isobutylene containing fractionv of the following composition:

Percent by volume was contacted with sulfuric acid at a temperature between 60 and 65 F. for approximately 30 minutes. About '7 volumes of the isobutylene fraction was admixed with about 3 volumes of the sulfuric acid. After the period of contact mentioned the hydrocarbon layer was separated from the acid layer which was withdrawn and stored at a reduced temperature of about 32 F.

Fifty eight volumes of the aforementioned propylene acid extract was heated to a temperature of 200 F. while agitating thoroughly. To this heated propylene extract was added 30 volumes of the cold isobutylene acid extract previously described. 'This second cold extract was added to the heated propylene acid extract slowly over a period of 20 minutes while agitatlog the mixture. It will be seen that the ratio of secondary olefin extract to tertiary olefin ex-' tract was approximately 1.9 to 1.

After the period of agitation mentioned, mixing was stopped and the hydrocarbon and acid layer allowed to separate under the influence of gravity into two layers: an acid layer and a hydrocarbon layer; the hydrocarbon layer was withdrawn from the mixing vessel and submitted for analysis. It was found that the polymer had an olefinic composition as follows:

Percent by volume 7 It will be noted that 71.5% of the polymer comprised olefinic hydrocarbons of 10 to 12 carbon atoms.

Th total polymer fraction, which had a bromine number of 108, was hydrogenated at 425 F. and at a hydrogen pressure of 1800 pounds per square inch over la, hydrogenation catalyst. The product from the hydrogenation had a bromine number of 1.4 The hydrogenated product was then distilled and separated into two fractions: one boiling between 150 and 325 F., and the other boiling between 325 and 369 F. Octane numbers of these two fractions were 84.5 and 85.8, respectively, indicating that both of them were suitable for inclusion in aviation fuel, the latter fraction being especially suitable for inclusion in a safety aviation fuel'on account of its high initial boiling point and high octane number. It is possible to increase further the octane number of the hydrogenated fraction by adding :tetraethyl lead thereto to obtain octane numbers of 100 or better. Usually not more than 4 cc. of lead is needed to obtain 100 octane number with a fuel having a' clear octane number in the range of 85.

While the present invention has been described in a specific example as a batch operation, it will "be apparent to the skilled worker that it is Within the scope of the invention to employ either batch or continuous operation. It is essential for best results that good contact between hydrocarbon and acid be obtained in forming the extract and that the secondary olefin extract be maintained in large excess to the tertiary olefin extract during the polymerization operation.

Having fully described and illustrated the practice of the present invention, what I wish to claim is:

1. A process for producing an interpolymerization product of a secondary olefin with a tertiary olefin which comprises the steps of forming a first extract by selectively absorbing a tertiary olefin'in sulfuric acid maintained at a temperature no greater than 125 F. to prevent substantial copolymerization of the tertiary olefin, forming a second extract by selectively absorbing a secondary olefin in sulfuric acid maintained at a temperature no greater than 125 F. to prevent substantial copolymerization of the secondary olefin, heating the second extract to a temperature of at least 150 F., mixing the heated second extract with the first extract in a mixing zone while maintaining a substantial excess of secondary olefin over tertiary olefin in the mixing zone and a temperature of at least 150 F. in the mixing zone to cause rapid interpolymerization of the secondary and tertiary olefin, removing product from the mixing zone and separating polymer therefrom.

2, A process in accordance with claim 1. in which a stream of first extract is admixed with a stream of second extract in the mixing zone and in which the product is removed continuously from the mixing zone.

3. A process in accordance with claim 1 in which the heated second extract is formed into a pool and into which first extract is added to the pool with intimate and rapid mixing.

4. A process for producing an interpolymerization product of isobutylene with propylene which comprises the steps of forming a first extract by absorbing isobutylene in sulfuric acid having a, strength in the range of 60 to 70 per cent and a temperature of F. forming a second extract by absorbing propylene in sulfuric acid having a strength in the range of to per cent and at a, temperature of 60 F., heating the second extract to a temperature in the range of to 250 F., mixing first extract with heated second 7 extract in a mixing zone and maintaining a large excess of propylene extract over isobutylene extract in the mixing zone to cause rapid interpolymerization, removing product from the mixing zone and separating polymer therefrom.

5. A process in accordance with claim 4 in which a stream of first extract and a stream of second extract are added continuously to the mixing zone and in which product is removed continuously from the mixing zone as a stream.

6. A process in accordance with claim 4 in which second extract is formed into a pool and the first extract is added to the pool with rapid an thorough admixture.

ORVAL A. BROWN.

REFERENCES CITED The following references file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Whitmore article in Jour. Amer. Chem. 800., vol. 63, Mar. 1941, pages 756-757.

are of record in the 

